Selectivity Control in Ruthenium(II)-Catalyzed C-H/N-O Activation with Alkynyl Bromides

C-H/N-O activation with 1-bromoalkynes was accomplished within a chemoselective ruthenium(II) catalysis manifold by means of carboxylate assistance. The exceedingly mild reaction conditions set the stage for the positional selective annulations of bromoalkynes at an ambient reaction temperature of 25 degrees C, placing the organic substituent distal to nitrogen in isoquinolones with a regioselectivity that is complementary to all previous protocols.